Gasoline production



April 9, 1940. c. M. HULL ET AL GASOLINE PRUDUCTION Filed oec. so, 19m

NXB o a.. m MMM fr masterape. o, 'i940 UNITED STATES' PATENT OFFICE x amasar I GAsoLiNE PnoDUc'rroN can Mei nun maroni n. Binner, chime, Ill., assignors to Standard Oil Company, Chicago, lll., a corporation of Application December ao, 1937, serial No. 132,556 11 claims. (ci. 19e-1o) This invention relates to gasoline production and it pertains more particularly to the preparation of high quality motor iuel from saturated hydrocarbon gases by conversion processes, pars ticuiariy by eiryiauon. n Aluminum chloride has long been known to be an important catalyst for the conversion of hydrocarbons into different form and for the synthesis of hydrocarbon products by combination l of lower molecular weight hydrocarbons. The

synthesis which comprises essentially the combination of a paramn with an olen gas is called yalkylatiou. We have found that saturated hydrocarbons, particularly isobutane, will react with '15 olens, particularly gaseous ,olefins such as ethylene, propylene or the butylenes, to yield normally liquid hydrocarbons vin the gasoline boiling range, which liquids are characterized by very high knock ratings (octane number).

catalyst for such alkylation reactions and to pro- Vvide an improved process for eiecting the alkylation.

Aluminum chloride which has heretofore been suggested as an alkylation catalyst is subject to the serious drawback that its catalytic activity is relatively short-lived. An object of ourv invention is to provide a catalyst and method of operation which will result in longer runs and better gasoline yields than have heretofore been obtained. Other objects will b e apparent from the following detailed description.

We have discovered in our work on the alkylation of isobutane with isobutylene at low temperatures that old samples oi aluminum chloride, samples containing appreciable quantities of alumina as an impurity, while producing a lower total yield of products, tended to give a higher percentage of the total product in the gasoline range than fresh samples of Al Cla. In other words. we have discovered that the catalyst for alkylation is not aluminum chloride, but. a mixture of alumina with aluminum chloride, the -latter being present in amounts of about 10% to 4 50%, preferably about 35%. This aluminaaluminum chloride catalyst mixture is .supplemented by the action of HCl which may be introduced as such or which may be liberated from the aluminum chloride by traces of moisture.v

chemical combination o fnormally gaseous hy- An 20 object of our invention is to provide an improved drocarbons, particularly the' combination of saturated hydrocarbons with unsaturated vhydrocarbons. A feature voi, our invention is our use of relatively low temperaturealiquid phase reaction conditions, and pressures slightly in excess n of the requirement to keep the reacting products in the liquid phase. While we prefer to operate our process in the liquid phase with corresponding low temperature range (-50 to +250 F.) and at relativelyV low pressures (15 to 600#/sq. in.), l0 nevertheless our process is operable in the vapor l phase at temperature ranges within the range of 100 to 500 F...and at pressures of 100# to 5000#/sq. in.

The invention will be more clearly understood 15 from the following detailed description and by reference to the accompanying drawing which forms a part of this disclosure and in which the single gure is a flow diagram of that part of the alkylation system in which our invention is y practiced.

The charging stock for our process may be a A mixture oli-saturated and unsaturated gases from any source whatsoever. We prefer to employthat fraction whichincludes the C2, Ca and C4 B5 hydrocarbons in petroleum renery gases. Such gases may bev obtained from a wide number oi sources such as cracking stills, stabilizers, ab-

sorbers, distillation units, etc. and the analysis of the gases may vary'withln'wide ranges. Pref- 80 erably the gases should contain about 25% to 50% olens such as ethylene, propylene and the butylenes, and it should contain among its saturated components as high a percentage as possible of iso-butane. Our process is. effective with I5 little or no isobutane but we prefer vto have 2% to 20% of isobutane in the feed stock. The saturated parafilns are not inert in our process as effected at temperatures oi ,-50 to +500 F., and

in operating a heat transfer medium vis passed 50 through heat exchanger VI3 to regulate the temperature ofthe-feed stock. We prefer to operate at as low a temperature as possible because oi' the more favorable'thermodynamic equilibria at I low temperatures. Howevenin-the case of rela- Iii tively inactive reactants it is necessary to employ higher temperatlues in order ito obtain appreciable yields in a reasonable length oi time. Thus, with the very reactive oleiin-para'in mixture, isobutylene-isobutane, we may eiiect alkylation at temperatures as low as F. and at essentially atmospheric pressure. On the other hand, with a feed such as ethylene-isobutane. mixture it may be necessary to operate at about 500 F. and at a pressure of 2000tt/sq. in. or higher, for example up to about 5000#/sq. in. in order to accomplish alkylation in a reasonable length of time.

The catalyst chamber `l5 is preferably in the form oi a heat exchanger consisting of a bundle of catalyst tubes I6 welded in. header plates l1 and surrounded by spaces i6 for heat transfer medium introduced through line I9 and discharged through line 20. The catalyst .in tubes I8 is preferably a mixture af alumina and aluminum chloride, which may be formed by admixing alumina with AlCla; the alumina may be in the form of crude bauxite ore or bauxite residues.'

The physical form of the catalyst should be such that it can come into intimate contact with hydrocarbon undergoing treatment, and it is immaterial if the catalyst contains other matters such as silica, clay, etc. The tubes are preferably loosely packed with this catalyst, preferably in the form of small pellets, with suitable screens or lters at each end of the tubes to prevent displacement of finely divided catalyst material.

Before the feed is introduced into the catalyst chamber we admix with it about 0.001% to1,0% of a halogen or halogen compound, -preferably HC1, although chlorine or organic halides may be employed if desired. Carbon tetrachloride is an excellent organic halide promoter, butwe prefer to use halides having low molecular weight alkyl radicals containing from aboutd to 8 carbon atoms so that on giving up the halogen content they become a part of the finished motor fuel. The halogen catalyst promoter is introduced through line 2| to line il at or near the point where this line discharges into the catalyst chamhalide catalyst promoter is-passed slowly through the catalyst tubes which are maintained at the desired reaction temperature by a heat transfer medium introduced through line i9 and dis.- charged through line 20. The reaction products leaving the system through line 22 pass through pressure release valve 22a and are then introduced into fractionator 2S which is supplied with conventional fractionating or bubble plates 24. a reflux coil 25, a reboiling coil 28 and trap-out plate 21. This tower is operated' under conditions of temperature and pressure to enable the withdrawal of gasoline from trap-out plate 21 through line 28, the withdrawal of heavy fractions from the base of the tower through line 29 and the withdrawal of uncondensed gases through line I0.. These gases Amay be further cooled in exchanger 3i and separated in tower 32 into light oil fractions which are withdrawn from the base of the tower through line 33, and gases whichniay be withdrawn from the. top of the tower through line 0d and returned by pump i5 through line 30 to line i2, or through line 31 to line M.

It should be understood that in our alkylation process the light fractions from line 83 may be recycled with incoming feedstock, particularly if the-feed stock is rich in oleilnic gases. We

- and freed from HCl if the fractionation system into a suitable scrubber into which water or a neutralizing fluid or absorber is introduced through line 40 and withdrawn, together with the HC1 through line ll, the gases being withdrawn from the system .through line 42. Similarly, the liquid products of our system may be neutralized does not accomplish this result to the desired extent. In both cas the recovered HC1. may be returned to the system if such recovery is warranted from an economic standpoint.

It should be understood that we may employ 20i any conventional type of catalyst chamber and we do not limit ourselves to the particular type herein disclosed. Similarly, the catalyst may be mounted on suitable carriers which may be solids or liquids.

'While' we have described in detail a preferred embodiment of our invention, it should be understood that we do not limit ourselves thereto except as defined by the following claims, which should be construed as broadly as the prior art will permit. v'

We claim: v

1. The method of reacting paraiiinlc and oleilnic hydrocarbon gases containing 2 to 4 carbon atoms per molecule to. form high quality motor fuel, which comprises treating a mixture of such paraiilnic and oleilnic hydrocarbon gases in a liquid'state under pressures of from 15 to 5000 pounds per square inch with a catalyst comprising alumina mixed with. 1050% AlCh supplemented by a promoter of the class consisting o! halogens, organic halides and halogen acids.

2. The method of claim 1 wherein the promoter is admixed with hydrocarbons prior to theircontact with the alumina-MC1: catalyst.

3. The method of claim 1 wherein thev reaction is eiected at a temperature below 0 F. and a pressure below BOO-pounds per square inch.

4. The method of converting a mixture of par-- aiilnic and oleilnlc hydrocarbon gases containing 50 'from about 2 to.'20% of isobutane to high quality motor fuel, which comprises liquefying said gases, introducing about .001 to 1.0% of a promoter of the class consisting of halogens, lorganic halides and halogen acids into the liqueiied gases, and, contacting said promoter-containing li'queiled mixture with alumina-A1013 catalyst under superatmospheric pressure to effect allrvlation.

5. The method of claim 4 wherein the reaction is eilected at temperatures below 0 F.

6. The method of making high quality motor fuel` outY of`oleiln-containing gases and parafnic hydrocarbon gases which comprises introducing asmall amount of a promoter of the class consisting of halogens, organic halides and halogen acids into a mixture of olefin-containing gases and paramnic hydrocarbon gases, and contacting said mixture with catalytically active alumina-Alfil: mixtures under-a pressure of from 70 15 to 5000 pounds per square inch.

7. The inethod of claim 6 wherein the reaction is eiected at temperatures not substantially higher than room temperatures. 8. The method of claim 8 wherein the reaction is eiiected at temperatures below 0 F.

9. The method of claim 6 wherein about 2 to a promoter oi' the class consisting ot chlorine, hy- 20% of the paraiiinic hydrocarbon gases consists 'drochloric acid and organic chlorides and conof isobutane. I tacting said mixturein the presence of said pro- 10. The method of claim 6 wherein the reacmoter with' a cataiyticaily active alumina-,alumi-y 5 tion is eii'ected at temperatures not higher than num chloride mixture under a. pressure of 15 to 6 500 F. .600 pounds per square inch, and atal temperature 11. The method oi making high quality gasonot substantially higherthan atmospheric temline from hydrocarbon gases 'containing propylperature. ene and butylenes admixed with propane, butane CARL MAX HULL. 10 and isobutane which comprises liquefying said hy-l FORD H; y BLUNCK. l0

drocarbon mixture, introducing into said mixture A v 

